Charge Delocalization in Self-Assembled Mixed-Valence Aromatic Cation Radicals

The spontaneous assembly of aromatic cation radicals (D+•) with their neutral counterpart (D) affords dimer cation radicals (D2+•). The intermolecular dimeric cation radicals are readily characterized by the appearance of an intervalence charge-resonance transition in the NIR region of their electronic spectra and by ESR spectroscopy. The X-ray crystal structure analysis and DFT calculations of a representative dimer cation radical (i.e., the octamethylbiphenylene dimer cation radical) have established that a hole (or single positive charge) is completely delocalized over both aromatic moieties. The energetics and the geometrical considerations for the formation of dimer cation radicals is deliberated with the aid of a series of cyclophane-like bichromophoric donors with drastically varied interplanar angles between the cofacially arranged aryl moieties. X-ray crystallography of a number of mixed-valence cation radicals derived from monochromophoric benzenoid donors established that they generally assemble in 1D stacks in the solid state. However, the use of polychromophoric intervalence cation radicals, where a single charge is effectively delocalized among all of the chromophores, can lead to higher-order assemblies with potential applications in long-range charge transport. As a proof of concept, we show that a single charge in the cation radical of a triptycene derivative is evenly distributed on all three benzenoid rings and this triptycene cation radical forms a 2D electronically coupled assembly, as established by X-ray crystallography

Modulation of Sn concentration in ZnO nanorod array: intensification on the conductivity and humidity sensing properties

Tin (Sn)-doped zinc oxide (ZnO) nanorod arrays (TZO) were synthesized onto aluminum-doped ZnO-coated glass substrate via a facile sonicated sol–gel immersion method for humidity sensor applications. These nanorod arrays were grown at different Sn concentrations ranging from 0.6 to 3 at.%. X-ray diffraction patterns showed that the deposited TZO arrays exhibited a wurtzite structure. The stress/strain condition of the ZnO film metamorphosed from tensile strain/compressive stress to compressive strain/tensile stress when the Sn concentrations increased. Results indicated that 1 at.% Sn doping of TZO, which has the lowest tensile stress of 0.14 GPa, generated the highest conductivity of 1.31 S cm− 1. In addition, 1 at.% Sn doping of TZO possessed superior sensitivity to a humidity of 3.36. These results revealed that the optimum performance of a humidity-sensing device can be obtained mainly by controlling the amount of extrinsic element in a ZnO film

Observation of the TeV gamma-ray source MGRO J1908+06 with ARGO-YBJ

The extended gamma ray source MGRO J1908+06, discovered by the Milagro air shower detector in 2007, has been observed for about 4 years by the ARGO-YBJ experiment at TeV energies, with a statistical significance of 6.2 standard deviations. The peak of the signal is found at a position consistent with the pulsar PSR J1907+0602. Parametrizing the source shape with a two-dimensional Gauss function we estimate an extension \sigma = 0.49 \pm 0.22 degrees, consistent with a previous measurement by the Cherenkov Array H.E.S.S.. The observed energy spectrum is dN/dE = 6.1 \pm 1.4 \times 10^-13 (E/4 TeV)^{-2.54 \pm 0.36} photons cm^-2 s^-1 TeV^-1, in the energy range 1-20 TeV. The measured gamma ray flux is consistent with the results of the Milagro detector, but is 2-3 times larger than the flux previously derived by H.E.S.S. at energies of a few TeV. The continuity of the Milagro and ARGO-YBJ observations and the stable excess rate observed by ARGO-YBJ along 4 years of data taking support the identification of MGRO J1908+06 as the steady powerful TeV pulsar wind nebula of PSR J1907+0602, with an integrated luminosity above 1 TeV about 1.8 times the Crab Nebula luminosity.Comment: 6 pages, accepted for pubblication by ApJ. Replaced to correct the author lis

Exposure–response relationship of AMG 386 in combination with weekly paclitaxel in recurrent ovarian cancer and its implication for dose selection

To characterize exposure-response relationships of AMG 386 in a phase 2 study in advanced ovarian cancer for the facilitation of dose selection in future studies.A population pharmacokinetic model of AMG 386 (N = 141) was developed and applied in an exposure-response analysis using data from patients (N = 160) with recurrent ovarian cancer who received paclitaxel plus AMG 386 (3 or 10 mg/kg once weekly) or placebo. Reduction in the risk of progression or death with increasing exposure (steady-state area under the concentration-versus-time curve [AUC(ss)]) was assessed using Cox regression analyses. Confounding factors were tested in multivariate analysis. Alternative AMG 386 doses were explored with Monte Carlo simulations using population pharmacokinetic and parametric survival models.There was a trend toward increased PFS with increased AUC(ss) (hazard ratio [HR] for each one-unit increment in AUC(ss), 0.97; P = 0.097), suggesting that the maximum effect on prolonging PFS was not achieved at the highest dose tested (10 mg/kg). Among patients with AUC(ss) ≥ 9.6 mg h/mL, PFS was 8.1 months versus 5.7 months for AUC(ss) < 9.6 mg h/mL and 4.6 months for placebo. No relationship between AUC(ss) and grade ≥ 3 adverse events was observed. Simulations predicted that AMG 386 15 mg/kg once weekly would result in an AUC(ss) ≥ 9.6 mg h/mL in > 90% of patients with median PFS of 8.2 months versus 5.0 months for placebo (HR [15 mg/kg vs. placebo], 0.56).Increased exposure to AMG 386 was associated with improved clinical outcomes in recurrent ovarian cancer, supporting the evaluation of a higher dose in future studies

Spatially restricted drivers and transitional cell populations cooperate with the microenvironment in untreated and chemo-resistant pancreatic cancer

Pancreatic ductal adenocarcinoma is a lethal disease with limited treatment options and poor survival. We studied 83 spatial samples from 31 patients (11 treatment-naïve and 20 treated) using single-cell/nucleus RNA sequencing, bulk-proteogenomics, spatial transcriptomics and cellular imaging. Subpopulations of tumor cells exhibited signatures of proliferation, KRAS signaling, cell stress and epithelial-to-mesenchymal transition. Mapping mutations and copy number events distinguished tumor populations from normal and transitional cells, including acinar-to-ductal metaplasia and pancreatic intraepithelial neoplasia. Pathology-assisted deconvolution of spatial transcriptomic data identified tumor and transitional subpopulations with distinct histological features. We showed coordinated expression of TIGIT in exhausted and regulatory T cells and Nectin in tumor cells. Chemo-resistant samples contain a threefold enrichment of inflammatory cancer-associated fibroblasts that upregulate metallothioneins. Our study reveals a deeper understanding of the intricate substructure of pancreatic ductal adenocarcinoma tumors that could help improve therapy for patients with this disease

Long-term Monitoring on Mrk 501 for Its VHE gamma Emission and a Flare in October 2011

As one of the brightest active blazars in both X-ray and very high energy $\gamma$-ray bands, Mrk 501 is very useful for physics associated with jets from AGNs. The ARGO-YBJ experiment is monitoring it for $\gamma$-rays above 0.3 TeV since November 2007. Starting from October 2011 the largest flare since 2005 is observed, which lasts to about April 2012. In this paper, a detailed analysis is reported. During the brightest $\gamma$-rays flaring episodes from October 17 to November 22, 2011, an excess of the event rate over 6 $\sigma$ is detected by ARGO-YBJ in the direction of Mrk 501, corresponding to an increase of the $\gamma$-ray flux above 1 TeV by a factor of 6.6$\pm$2.2 from its steady emission. In particular, the $\gamma$-ray flux above 8 TeV is detected with a significance better than 4 $\sigma$. Based on time-dependent synchrotron self-Compton (SSC) processes, the broad-band energy spectrum is interpreted as the emission from an electron energy distribution parameterized with a single power-law function with an exponential cutoff at its high energy end. The average spectral energy distribution for the steady emission is well described by this simple one-zone SSC model. However, the detection of $\gamma$-rays above 8 TeV during the flare challenges this model due to the hardness of the spectra. Correlations between X-rays and $\gamma$-rays are also investigated.Comment: have been accepted for publication at Ap

Zinc oxide hierarchical nanostructures as potential NO2 sensors

A superficial thermal evaporation method has been employed for the fabrication of hierarchical zinc oxide (ZnO) nanostructured films, composed of nanorods (NR's) and bunch of nanowires (BNW's), on glass substrate and the diverse atmospheric annealing effect on their structural, morphological, compositional, and gas sensing properties has been systematically studied and reported. Structural investigation corroborates the formation of crystalline hexagonal wurtzite ZnO. The arrays of vertically aligned nanorods and bunch of nanowires of ZnO were observed on the substrate surface. As-prepared ZnO NR's and BNW's are utilized as a sensing material for detection of toxic nitrogen dioxide (NO2). The ZnO sensors exhibit high response to NO2 along with rapid response and recovery time values @200 degrees C. In addition, ZnO sensors respond to a very small exposure of NO2 gas i.e. 1 ppm. Furthermore, the developed sensors attain excellent stability and reproducibility in response. Finally, the interaction of NO2 gas molecules with hierarchical nanostructured ZnO sensors has successfully been studied and discussed by employing an electrochemical impedance spectroscopy measurement

Thermally evaporated copper oxide films: A view of annealing effect on physical and gas sensing properties

The present paper reports a facile approach to prepare copper oxide (CuO) films directly onto a glass substrate by thermal evaporation method and their chemiresistive properties towards hazardous nitrogen dioxide (NO2). The influence of annealing temperature on structural, morphological, and gas sensing properties of the CuO films has been thoroughly investigated and reported. Structural and morphological analyses has confirmed the formation of polycrystalline monoclinic CuO with uniformly distributed nanoparticles over the substrate surface. Gas sensing measurements on CuO films reveal the high response, excellent selectivity, fast response recovery time signatures, good repeatability, and stability towards lower concentration of NO2 gas @150 C-circle. A maximum response of 48% towards 100 ppm NO2 has been achieved. Gas sensing results demonstrate an influence of morphology on the NO2 sensing performance of CuO films. In addition, the interactions between CuO sensor film and NO2 gas molecules are studied through an impendence spectroscopy analysi

Topical minoxidil fortified with finasteride: An account of maintenance of hair density after replacing oral finasteride

Background: Finasteride acts by reducing dihydrotestosterone levels, thereby inhibiting miniaturization of hair follicles in patients with androgenetic alopecia (AGA). Oral finasteride is associated with side effects such as decreased libido, sexual dysfunction, and gynecomastia. Aim: The aim of the following study is to assess the efficacy of maintaining hair growth with 5% topical minoxidil fortified with 0.1% finasteride in patients with AGA after initial treatment with 5% topical minoxidil and oral finasteride for two years. Materials and Methods: A retrospective assessment was done in 50 male patients aged 20-40 years with AGA. All the patients had been initially treated with topical minoxidil and oral finasteride for a period of two years, after which the oral finasteride was replaced with topical minoxidil fortified with finasteride. Five of 50 patients had discontinued the treatment for a period of 8-12 months and were then resumed with only topical minoxidil fortified with finasteride. The patients′ case sheets and photographs were reviewed by independent observers and the efficacy of minoxidil-finasteride combination was assessed. Results: Of the 45 patients who underwent a continuous treatment for AGA, 84.44% maintained a good hair density with topical minoxidil-finasteride combinatio. Of the five patients who discontinued oral finasteride for 8-12 months, four demonstrated good improvement in hair density when treatment was resumed with topical minoxidil-finasteride combination. Conclusion: Topical finasteride can be considered for hair density maintenance after initial improvement with oral finasteride, thereby obviating the indefinite use of oral finasteride